Comprehensive profiling and evaluation of free/conjugated Phytosterols in crops using chemical derivatization coupled with UHPLC-ESI-QTOF-MS/MS

• Published in: Food chemistry 2025-01, Vol.463 (Pt 3), p.141316, Article 141316
• Main Authors: Xu, Qiuhui, Wang, Dan, Lv, Xin, Chen, Hong, Wei, Fang
• Format: Article
• Language: English
• Subjects: Chromatography, High Pressure Liquid; Crops, Agricultural - chemistry; Detection sensitivity; Distinctive marker; DNSCl derivatization; Phytosterol profile; Phytosterols - analysis; Phytosterols - chemistry; Precursor ion scanning; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry
• ISSN: 0308-8146; 1873-7072; 1873-7072
• DOI: 10.1016/j.foodchem.2024.141316

Phytosterols are naturally existed in crops but their detection is constrained by sensitivity and accuracy due to the inefficient analytical approaches. This study hypothesizes that an untargeted analytical method combining chemical derivatization with ultrahigh performance liquid chromatography-electrospray ionization quadrupole time-of-flight mass spectrometry can identify the various composition and contents of phytosterols in different crops. The results showed that chemical derivatization significantly enhanced intensity of phytosterols compared with non-derivatized samples. Using precursor ion scanning (PIS) of m/z 252.0690, dansyl chloride-labeled phytosterols were identified, demonstrating that rapeseeds had the highest content of total phytosterol (3981.2 ± 95.3 mg/kg), followed by sunflower seeds, flaxseeds, corn and rice, respectively. Principal component analysis revealed significant variations in phytosterol distribution among 15 crop samples, suggesting the applicability of phytosterol profile as a marker for phytosterols-contained crops. Hence, the proposed analytic approach proves high efficiency and accuracy in determining phytosterols and advances the study for phytosterol-enriched crops. •UHPLC-ESI-QTOF-MS/MS coupled with derivatization enhances phytosterol detection.•Chemical derivatization significantly boosts phytosterol MS intensity.•Precursor ion scanning of m/z 252.0690 could identify DNSCl-labled phytosterols.•Rapeseed has the highest total phytosterol content at 3981.15 ± 95.26 mg/kg.•Distinct phytosterol profiles revealed PCA can be used for unique markers.